US6246156B1 - Piezoelectric/electrostrictive element - Google Patents

Piezoelectric/electrostrictive element Download PDF

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US6246156B1
US6246156B1 US09/276,580 US27658099A US6246156B1 US 6246156 B1 US6246156 B1 US 6246156B1 US 27658099 A US27658099 A US 27658099A US 6246156 B1 US6246156 B1 US 6246156B1
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piezoelectric
electrostrictive
phase
ceramic substrate
tetragonal
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Yukihisa Takeuchi
Koji Kimura
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NGK Insulators Ltd
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Definitions

  • the present invention relates to unimorph- and bimorph-type piezoelectric/electrostrictive elements used as various transducers and various actuators.
  • a piezoelectric/electrostrictive element is used in various fields such as various transducers for converting electrical energy into mechanical energy, that is, electrical energy into mechanical displacement, force, or vibration, and vice versa, various actuators, frequency-region functional components including various actuators and filters, various display devices including displays, sounding bodies including loudspeakers, microphones, and sensors including ultrasonic sensors.
  • a piezoelectric/electrostrictive element comprising a film-type piezoelectric/electrostrictive operating portion 5 constituted with a ceramic substrate 1 serving as a diaphragm and a first electrode film 2 , a piezoelectric/electrostrictive film 3 , and a second electrode film 4 formed on the ceramic substrate 1 (Japanese Patent Application Laid-Open No. 3-128681) as shown in FIG.
  • a piezoelectric/electrostrictive element in which a ceramic substrate has a cavity, the bottom of the cavity is constituted so as to be a thin-wall portion, and a piezoelectric/electrostrictive operating portion is integrated on the outer surface of the thin-wall portion (Japanese Patent Application Laid-Open No. 5-49270) as shown in FIG 1 ( b ).
  • a ceramic substrate using zirconium oxide partially stabilized with yttrium oxide is generally known as the ceramic substrate constituting a piezoelectric/electrostrictive element 7 (Japanese Patent Application Laid-Open Nos. 5-29675, 5-97437, and 5-270912).
  • a crack maybe recognized at a specific portion, that is, at a portion of ceramic-substrate 1 near the boundary of the first electrode film 2 as shown in FIGS. 2 ( a ) and 2 ( b ) particularly through heat treatment (firing) for integrating the piezoelectric/electrostrictive film 3 with the first electrode film 2 and the ceramic substrate 1 depending on the firing condition, and thereby a problem occurs that the production yield is lowered.
  • the yttrium oxide is decreased because the above portion is a portion which piezoelectric/electrostrictive film 3 directly contacts the ceramic substrate 1 when the piezoelectric/electrostrictive film 3 protrudes over the first electrode film 2 on the ceramic substrate 1 in order to prevent a short circuit from occurring between upper and lower electrodes, the yttrium oxide selectively diffuses to the piezoelectric/electrostrictive film 3 when the film 3 is sintered and integrated.
  • the vicinity of the boundary of the first electrode film 2 on the ceramic substrate 1 is a portion to which a large stress is easily applied to integrate the piezoelectric/electrostrictive film 3 , first electrode film 5 , and ceramic substrate 1 through heat treatment.
  • the stress under the heat treatment causes a decrease in the yttrium oxide because the stress becomes high particularly in the cavity structure.
  • crystal phase transformation of zirconium oxide is induced due to a decrease in the yttrium oxide and this results in the crack formation.
  • the partially stabilized zirconium oxide particularly the zirconium oxide partially stabilized with 2 to 4 mol % of yttrium oxide
  • the partially stabillized zirconium oxide is susceptible to crystal phase transformation and cracking if the amount of yttrium oxide serving as a stabilizer is decreased due to any factor while sintering the piezoelectric/electrostrictive film 3 as described above.
  • the above problem is peculiar to a piezoelectric/electrostrictive element constituted by integrating a ceramic substrate serving as a diaphragm with a film-type piezoelectric/electrostrictive operating portion through heat treatment without using an adhesive or the like.
  • the present invention is made to solve the above problems and its object is to provide an advanced-functional and high-performance piezoelectric/electrostrictive element that uses the strength of a ceramic substrate (diaphragm) and preventing a crack from being produced due to an internal factor when firing a piezoelectric/electrostrictive film.
  • the present invention provides a piezoelectric/electrostrictive-film-type element comprising: a ceramic substrate having a material whose main component is zirconium oxide and at least one film-type piezoelectric/electrostrictive operating portion comprising a first electrode film, a piezoelectric/electrostrictive film, and a second electrode film on the ceramic substrate; wherein the ceramic substrate comprises a base layer and a surface layer, and the crystal phase of the zirconium oxide of the base layer is a tetragonal phase or a mixed crystal phase of tetragonal and cubic phase, tetragonal and monoclinic phase, or tetragonal, cubic, and monoclinic phase, and the crystal phase of the zirconium oxide of the surface layer is mainly a cubic phase, and the piezoelectric/electrostrictive operating portion is formed on the surface layer.
  • the zirconium oxide of the surface layer is stabilizedwith 6 to 20 mol % of yttrium oxide.
  • the zirconium oxide of the base layer is partially stabilized with 2 to 4 mol % of yttrium oxide.
  • the crystal grain size of the zirconium oxide in the base layer is held within a range of 0.1 and 1.5 ⁇ m.
  • the thickness of a ceramic substrate is preferably set to 50 ⁇ m or less. Therefore, it is possible to thicken the portion where the diaphram is not present, that is, where, a piezoelectric/electrostrictive operating portion is not formed, and thereby, advantageously handle the ceramic substrate. Moreover, even when arranging devices adjacent to one another, it is possible to set a thick wall portion between elements and this is advantageous in preventing mutual interference between characteristics of the elements.
  • FIG. 1 ( a ) is a perspective view of a conventional piezoelectric/electrostrictive element and FIG. 1 ( b ) is a perspective view of another conventional piezoelectric/electrostrictive element.
  • FIG. 2 ( a ) is a sectional view of the crack occurrence portion of FIG. 1 ( a ), taken along the line A—A of FIG. 1 ( a ) and FIG. 2 ( b ) is a sectional view of the crack occurrence portion of FIG. 1 ( b ), taken along the line B—B of FIG. 1 ( b ).
  • FIG. 3 ( a ) is a schematic sectional view of a piezoelectric/electrostrictive element of the present invention
  • FIG. 3 ( b ) a schematic sectional view of another piezoelectric/electrostrictive element of the present invention.
  • FIG. 4 is a perspective view of another piezoelectric/electrostrictive element of the present invention.
  • a ceramic substrate 1 having a material whose main component is zirconium oxide comprises a base layer 10 and a surface layer 9 , and the surface layer 9 , on which a piezoelectric/electrostrictive operating portion 5 is formed, mainly comprises zirconium oxide whose main crystal phase is cubic phase.
  • the cubic phase is a stable crystal phase and it does not easily cause phase transformation even if yttrium oxide decreases due to the firing environment of the piezoelectric/electrostrictive operating portion 5 or the stress or diffusion caused in firing the portion 5 . Therefore, it is possible to effectively prevent a crack from occurring in the ceramic substrate 1 nearby the boundary of a first electrode film 2 .
  • a base layer 10 of a ceramic substrate 1 mainly comprises zirconium oxide which is a tetragonal phase or a mixed phase of tetragonal and cubic phase, tetragonal and monoclinic phase, or tetragonal, cubic, and monoclinic phase. Because the tetragonal phase or mixed phase of tetragonal and cubic phase, tetragonal and monoclinic phase, ortetragonal, cubic, and monoclinic phase is superior in toughness and strength, it is possible to provide a mechanical strength for the ceramic substrate 1 . Therefore, a piezoelectric/electrostrictive element having excellent functional characteristic and productivity is realized.
  • a main component in this application represents a component having a weight percentage of 85% or more.
  • identification and ratio calculation of each crystal phase included in a crystal system is performed in accordance with the X-ray diffraction method or Raman spectroscopy.
  • the X-ray diffraction method is used to obtain the content ratio of each crystal phase in accordance with the intensity ratio between typical diffraction peaks of the crystal phases.
  • the content ratio of cubic phase is defined by the content ratio of the cubic phase to each crystal phase and the content of cubic phase is obtained in accordance with the intensity ratio between main diffraction peaks of the crystal phases.
  • the expression “mainly cubic phase” represents meeting the following relation. I ⁇ C ⁇ ( 111 ) I ⁇ M ⁇ ( 1 _ ⁇ 11 ) + I ⁇ C ⁇ ( 111 ) + I ⁇ T ⁇ ( 111 ) ⁇ 0.70 , ⁇ preferably ⁇ 0.9
  • each diffraction-peak intensity is obtained as 25 and 43 (sum of (002) and (200)) to the main (111) diffraction-peak intensity 100 in accordance with the JCPDS card.
  • I.T (002) Diffraction intensity of (002) of tetragonal phase
  • the total thickness (base layer+surface layer) of the ceramic substrate 1 is 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 15 ⁇ m or less in order to maintain the quick-response characteristic of the piezoelectric/electrostrictive element and from the viewpoint of the amount of displacement, generation force, or sensitivity of the element.
  • the ratio between the thicknesses of the base layer 10 and surface layer 9 is set to 6:4 to 8:2.
  • the surface layer 9 For the surface layer 9 to have a crystal phase that is mainly cubic phase, it is preferable to stabilize zirconium oxide in the surface layer by addition of 6 to 20 mol %, more preferably 7 to 10 mol % of yttrium oxide to the layer 9 .
  • the base layer 10 to have a crystal phase a tetragonal phase or mixed phase of tetragonal and cubic phase, tetragonal and monoclinic phase, or tetragonal, cubic, and monoclinic phase, it is preferable to stabilize zirconium oxide in the base layer 10 by addition of 2 to 4 mol %, more preferably 2.5 to 3.5 mol % of yttrium oxide to the layer 10 .
  • the crystal grain size of the zirconium oxide of the base layer 10 is held within a range of 0.1 and 1.5 ⁇ m and more preferable that the size is 1.0 ⁇ m or less. By setting the crystal grain size to the above range, it is possible to obtain a large strength even for a small thickness and moreover, stably form a predetermined crystal phase.
  • silicon oxide SiO or SiO 2
  • a sintering aid such as clay
  • the reaction with a material constituting a piezoelectric/electrostrictive operating portion increases under heat treatment of the piezoelectric/electrostrictive operating portion and it is difficult to control the composition of the piezoelectric/electrostrictive operating portion, especially that of the piezoelectric/electrostrictive film. Therefore, it is necessary to set the content of silicon oxide to less than 1 wt %.
  • a plurality of piezoelectric/electrostrictive elements are formed on a relatively large ceramic substrate 1 .
  • a piezoelectric/electrostrictive element of the present invention may be manufactured as described below.
  • the ceramic substrate 1 is made by separately manufacturing green sheets for the base and surface layers that are composed of a predetermined material respectively by a doctor blade or reverse roll coater, superimposing them on each other while applying heat and pressure, and firing them at a temperature of 1,200 to 1,600° C.
  • the ceramic substrate 1 by forming a surface layer on a green sheet for the base layer through screen printing, spraying, or coating method by using a slurry or paste serving as a surface-layer material (it is also possible to form a surface layer only on the portion on which a piezoelectric/electrostrictive operating portion is formed) and similarly firing the ceramic substrate 1 or it is possible to make the ceramic substrate 1 by forming a base layer on a green sheet for the surface layer through screen printing, spraying, or coating method.
  • a green sheet provided with one opening such as an aperture or cutout formed through its thickness serving as a cavity is prepared by using a die and a machining method such as ultrasonic machining in addition to the green sheet for the diaphragm (for the base and surface layers) to similarly superimpose both the green sheets on each other while applying heat and pressure and fire them. Furthermore, it is possible to form the ceramic substrate into a cavity structure provided with a member for closing an opening at an opposite side to the diaphragm.
  • the piezoelectric/electrostrictive operating portion 5 is formed on the ceramic substrate 1 by using a thick-film forming method such as screen printing, spraying, dipping, coating and electrophoresis, or a thin-film forming method such as ion-beam, sputtering, vacuum evaporation, ion plating, CVD, and plating.
  • a thick-film forming method such as screen printing, spraying, dipping, coating and electrophoresis
  • a thin-film forming method such as ion-beam, sputtering, vacuum evaporation, ion plating, CVD, and plating.
  • a thick-film forming method such as screen printing, spraying, dipping, coating and electrophoresis method is preferably used to form a piezoelectric/electrostrictive film.
  • a method for forming a pattern by using one of screen printing, photolithography, laser processing method such as excimer or YAG, and a method for forming a pattern by using a machining method such as ultrasonic machining or slicing and thereby removing unnecessary portions is used.
  • a temperature for heat-treating to integrate the film and ceramic substrate thus formed within a range of 900 to 1,400° C., more preferably, within a range of 1,000 to 1,400° C. is advantageously selected.
  • any material can be used for the first electrode film 2 constituting the piezoelectric/electrostrictive operating portion 5 as long as the material is a conductor capable of withstanding a high-temperature and an oxidation environment such as the above heat-treatment temperature and firing temperature.
  • the material is a conductor capable of withstanding a high-temperature and an oxidation environment such as the above heat-treatment temperature and firing temperature.
  • noble metals having a high melting point such as platinum, palladium, and rhodium
  • an electrode material mainly containing an alloy of silver and palladium, silver and platinum or platinum and palladium cermet made of platinum and a ceramic substrate material, cermet made of platinum and a piezoelectric material, and cermet made of platinum, a substrate material, and a piezoelectric material.
  • cermet made of platinum and a ceramic substrate material cermet made of platinum and a piezoelectric material
  • cermet made of platinum, a substrate material, and a piezoelectric material it is more preferable to use a material containing platinum as a main component.
  • the material of the second electrode film 4 is not restricted. It is possible to use one of the materials used as the first electrode film 2 , gold, chromium, copper or the like formed by sputtering, or gold or silver film using resinate material.
  • the piezoelectric/electrostrictive film 3 constituting the piezoelectric/electrostrictive operating portion 5 it is possible to use any material as long as the material shows an electric field induced strain such as a piezoelectric or electrostrictive effect.
  • the piezoelectric/electrostrictive material maybe either a crystalline material or an amorphous material, and may be a semi-conductor material or a dielectric, ferroelectric ceramic or anti-ferroelectric ceramic material.
  • the piezoelectric/electrostrictive material may either require a treatment for initial polarization or poling, or may not require such a polarization treatment.
  • piezoelectric/electrostrictive materials used for the present invention the following materials are specifically listed: a material whose main component is lead zirconate titanate (PZT), lead titanate, lead zirconate, lead magnesium niobate (PMN), lead nickel niobate (PNN), lead magnesium tungstate, lead manganese niobate, lead antimony stannate, lead zinc niobate, lead magnesium tantalate, lead nickel tantalate, and a composite material of the above materials.
  • PZT lead zirconate titanate
  • PMN lead magnesium niobate
  • PNN lead nickel niobate
  • lead magnesium tungstate lead manganese niobate
  • lead antimony stannate lead zinc niobate
  • lead magnesium tantalate lead nickel tantalate
  • lead nickel tantalate lead nickel tantalate
  • oxides of lanthanum, barium, niobium, zinc, cerium, cadmium, chromium, cobalt, antimony, iron, yttrium, tantalum, tungsten, nickel, manganese, lithium, strontium, magnesium, calcium, bismuth, tin, and a compound of these substances to above mentioned materials.
  • a PLZT-based material obtained by addition of the oxide of lanthanum to a PZT-based material.
  • a material whose main component is a mixture of lead magnesium niobate, lead zirconate, and lead titanate
  • a material whose main component is a mixture of lead nickel niobate, lead magnesium niobate, lead zirconate, and lead titanate
  • a material whose main component is the mixture of lead nickel tantalate, lead magnesium niobate, lead zirconate, and lead titanate
  • a material whose main component is a mixture of lead magnesium tantalate, lead magnesium niobate, lead zirconate, and lead titanate
  • a material whose main component is a mixture of lead magnesium tantalate, lead magnesium niobate, lead zirconate, and lead titanate.
  • a material whose main component is the mixture of lead magnesium niobate, lead zirconate, and lead titanate is preferably used. Because this material not only has a high piezoelectric constant but is also particularly less relative with a substrate material during heat treatment.
  • the piezoelectric/electrostrictive characteristics are changed depending on the composition of a component.
  • a ternary system material made of lead magnesium-niobate, lead zirconate, and lead titanate preferably used for a piezoelectric/electrostrictive element of the present invention
  • a composition nearby the phase boundary between pseudo-cubicphase, tetragonal phase, and rhombohedral phase is preferable.
  • a composition containing 15 to 50 mol % of lead magnesium niobate, 10 to 45 mol % of lead zirconate, and 30 to 45 mol % of lead titanate is preferably used because the composition has a high piezoelectric constant and a high electromechanical coupling factor.
  • a piezoelectric/electrostrictive element of the present invention is preferably used for various transducers for converting electrical energy into mechanical energy, that is, a mechanical displacement, force, or vibration, and vice versa, various actuators, frequency-region functional parts including filters, various indication devices including displays, transformers, sounding bodies including microphones and loudspeakers, vibrators, resonators, or oscillators for communication or motive power, discriminators, various sensors including ultrasonic sensors, acceleration sensors, angular velocity sensors, impact sensors, and mass sensors, gyros, and moreover a unimorph-type device and a bimorph-type device used for the servo shift device, pulse driven motor, ultrasonic motor, piezoelectric fan, and piezoelectric relay described in “From foundation to application of piezoelectric/electrostrictive actuator” written by K. Uchino, (Edited by NIPPON KOGYOGIJUTSU CENTER), (MORIKITA SHUPPAN)”, and more preferably used for various actuators,
  • a piezoelectric/electrostrictive element of the present invention can be used as a film-type capacitor device because it has not only the piezoelectric/electrostrictive characteristic but also dielectricity.
  • a piezoelectric/electrostrictive element of the present invention is described above on the basis of a unimorph structure constituting a piezoelectric/electrostrictive operating portion at only one side of a ceramic substrate. It is a matter of course that a piezoelectric/electrostrictive element of the present invention can be also applied to a bimorph structure constituting the piezoelectric/electrostrictive operating portion at both sides of the ceramic substrate. In this case, the surface layers are formed on both sides of the base layer.
  • a piezoelectric/electrostrictive element 7 shown in FIG. 3 ( b ) was manufactured in which a ceramic substrate was constituted with a base layer and a surface layer and had a cavity.
  • the base layer 10 was made of zirconium oxide which crystal phase was tetragonal phase obtained by addition of 3 mol % of yttrium oxide and the surface layer 9 was made of zirconium oxide obtained by addition of 7 mol % of yttrium oxide.
  • the value of a conditional expression is 0.90.
  • a piezoelectric/electrostrictive operating portion 5 was formed on the surface layer 9 .
  • a surface layer was formed on the surface of a green sheet for the base layer by using a paste material for the surface layer by means of screen printing.
  • the green sheet for the base layer and the surface layer were set so that the thickness of the base layer became 6 ⁇ m and that of the surface layer became 2 ⁇ m after they were fired.
  • a first electrode film 2 was made of platinum
  • a piezoelectric/electrostrictive film 3 was made of a material whose main component is a mixture of lead zirconate, lead titanate, and lead magnesium niobate
  • a second electrode film 4 was made of gold.
  • the piezoelectric/electrostrictive operating portion 5 was formed by means of screen printing.
  • the first electrode film 2 was fired at 1,300° C.
  • the piezoelectric/electrostrictive film 3 was fired at 1,250° C.
  • the second electrode film 4 was fired at 600° C.
  • the thickness of the first electrode film 2 was set to 3 ⁇ m
  • that of the piezoelectric/electrostrictive film 3 was set to 14 ⁇ m
  • that of the second electrode film 4 was set to 0.5 ⁇ m.
  • piezoelectric/electrostrictive elements 7 were manufactured to evaluate whether a crack occurred in a ceramic substrate 1 by using a crack-inspection penetrant. Table 1 shows a result of the evaluation.
  • Example 1 Zirconium oxide obtained by addition of 10 mol % of yttrium oxide to a surface layer 9 was used.
  • One thousand piezoelectric/electrostrictive elements were manufactured by the same manner as the case of Example 1 except that the value of a conditional expression was 1 to evaluate whether a crack occurred in a ceramic substrate 1 in the same manner as the case of Example 1.
  • Table 1 shows a result of the evaluation.
  • Example 1 Zirconium oxide obtained by addition of 6 mol % of yttrium oxide to a surface layer 9 was used.
  • One thousand piezoelectric/electrostrictive elements were manufactured by the same manner as the case of Example 1 except that the value of a conditional expression was 0.80 to evaluate whether a crack occurred in a ceramic substrate 1 in the same manner as the case of Example 1.
  • Table 1 shows a result of the evaluation.
  • a piezoelectric/electrostrictive element 7 shown in FIG. 1 ( b ) was manufactured in which a ceramic substrate was constituted with a single layer and had a cavity.
  • the ceramic substrate was made of zirconium oxide which crystal phase was tetragonal phase obtained by addition of 3 mol % of yttrium oxide.
  • a piezoelectric/electrostrictive operating portion 5 was formed on the surface of the ceramic substrate 1 at the opposite side to the side with which a support member 6 was connected.
  • An opening was formed on a green sheet for a supporting member in order to form a cavity of 0.2 mm ⁇ 4 mm and then, the green sheet for the supporting member and a green sheet for the ceramic substrate were superimposed on each other while applying heat and pressure, and fired at 1,500° C.
  • the thickness of a ceramic substrate after firing was set to 8 ⁇ m.
  • a piezoelectric/electrostrictive operating portion 5 was formed on the ceramic substrate.
  • the material and the thickness of each layer of the piezoelectric/electrostrictive operating portion 5 were the same as those of Example 1.
  • a ceramic substrate comprises a base layer and a surface layer and the surface layer of the ceramic substrate on which the piezoelectric/electrostrictive operating portion is formed is made of the material whose main component is zirconium oxide which crystal phase is mainly cubic phase Therefore, a crack does not easily occur in the ceramic substrate nearby the boundary of a first electrode film.
  • the base layer of the ceramic substrate is made of a material whose main component is zirconium oxide which crystal phase is a tetragonal phase or a mixed phase of tetragonal and cubic phase, tetragonal and monoclinic phase, or tetragonal, cubic, and monoclinic phase, it is possible to keep a high mechanical strength even with a small thickness. Therefore, it is possible to completely show the excellent characteristics in the function as a substrate (diaphragm) for a film type piezoelectric/electrostrictive element and provide a high performance piezoelectric/electrostrictive element.

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